Hydrogen generation.



C. ELLIS. HYDROGEN GENERATION. APPLICATION FILED JUNE 6,1913.

1 1 '73 ,4 l '7 Patented Feb. 29, I916.

I E I dafi z;

HYDROGEN GENERATION.

Specification of Letters Patent.

Patented Feb. 29, 1916.

Application filed June 6, 1913. Serial No. 772,049.

To all whom it may concern:

Be it known that I, CARLE'roN ELLIS, a citizen of the United States, anda resident of Montclair, in the county of Essex and State of New Jersey,haveinvented certain new and useful Improvements in Hydrogen Generation,of which the following is a specification.

This invention relates to a method of making hydrogen and relates inparticular to a process involving the treatment of lime or lime-materialwith carbon monoxid, or carbon monoxid containing gases; or carbonmaterial such as oil vapors and the like, capable under certaincircumstances, of producing carbon monoxid.

When carbon monoxid is passed over hydrated lime or carbon monoxidmingled with steam is passed over. quick lime, the latter being heatedto a temperature of 450600 (1.; the monoxid takes oxygen from thewatervapor forming carbon dioxid and liberating hydrogen, the carbon monoxidcombining with the lime to form calcium carbonate. This action isaccelerated by the presence of catalytic material such as iron oxid andmanganese oxid. The reaction produces heat or is exothermic so that whenonce the mass of lime has been brought to the reacting temperature,sufiicient heat often is developed for continuance of the operationwithout the aid of externally applied heat. In fact cooling maysometimes be required as the reaction does not progress with as goodyields when the temperature is much above 525 or 550 C.Anotherconsideration in this connection is the use of an excess of steamwhich greatly improves the yield of the hydrogen and greatly decreasesthe residue of any carbon monoxid. Preferably 4 to 5 times as much watervapor by volume as-carbon monoxid should be present in order to eflectthe desired substantially complete conversion. Difiiculties areexperienced in treatinglime with gases to insure satisfactory absorptionof the carbon dioxid, and it is desirable to remove-the carbon dioxid asfast as it is formed in order to prevent by mass action the repressionof the reaction due to the accumulation of the carbon dioxid in thegaseous atmosphere.

To carryout the conditions -required for the reaction as specified, andto practise the present invention in its preferred embodiment, I makeuse of the illustrative apparatus diagrammatically depicted in theaccompanying drawing which shows mainly in vert1cal section a treatingapparatus comprising a series of superimposed conveyers;

a portion of the conveying conduits being shown in elevation.

In the drawings 1 is a' furnace wall supporting a series of conveyingconduits equipped with spiral conveyers or similar conveying devices,these being shown at 2, 2 2 and 2. These conveyers are connected bychutes so that material entering the upper conveyer feeds downwardlyconveyer by conveyer until it passes from the lower section.

3, 3 and 3 are partitions or bailles separating more or less the severalconveyer sections and enabling differing temperatures if desired to bemaintained in different sections.

4 is a small feeding conveyer connecting with the supply hopper 5 at oneend and communicating at the other end with the conveyer 2.

6 is an outlet pipe from 2 communicating with the receptacle 7 havingthe discharging conveyer 8. The material collecting in the receptacle 7is shown at 9.

10 is an inlet for water-gas or other gas or vapor and 11 is an exit forsuch gases. 12 is a port through which combustible gases for heatingpurposes or heated prodnets of combustion may be introduced to raise thetemperature of the sections to the requisite degree. 12 and 12 aresimilar ports. Through these ports cold air may also be admitted inorder to cool the vapors in case the temperature becomes excessive.

.The operation of the apparatus is as follows: The lime material isplaced in the hopper 5 and is fed by the conveyer 4 into the conveyer 2,traveling along the conveyer 2 and passing into the conveyer 2*, theninto 2 and 2 and finally discharging into the'receptacle 7. By means ofthe pipe 10 a mixture, 1 0 for example, of water-gas and steampreferably in the proportion of 1 part of watergas' to from 222; partsof steam is introduced and this mixture may be preheated if desired. Thegaseous mixture and vapors pass over the lime material discharging fromthe section 2 and become preheated to the reacting temperature so thatat least by the, time they have entered the section 2", preferably theyare heated to the required reacting temperature which is approximately500 C. The gas or vapor mixture passes from section to section incontact with lime materlal which is being constantly but slowly movedforward in a direction opposite to the flow of the gases or vapors andin this manner the carbon monoxid uniting with the oxygen of thewaterforms' carbon dioxid which combines with the lime, removing thecarbon dioxid as such from the scene of the reaction and enabling afurther conversion of carbon monoxid into carbon dioxid, so that thegases discharging from the upper section of the conveyer may bepractically pure hydrogen or hydrogen containing only a small measure ofcontaminating products. I

The lime which is employed forthe o eration preferably is as low inmagnesia, as

dolomite and other high magnesia limes are not as desirable for thispurpose. Preferably the lime should-be finelydivided which may beaccomplished by grinding same, or the lime may be introduced in thehydrated form as a dry powder. In any and preferably passed through arotary kiln.

event the addition of 5% or so of finely divided iron or manganese oxidis desirable,

as promoting the reaction in a very large measure. The iron or manganeseoxid preferably is derived by precipitation as a hydrate from aqueoussolution and washing and drying the product.

The carbonated lime discharging into the receptacle 7 is removed. by theconveyor 8 which may be heated by a producer gas or a powdered coalflame, and the lime rcgens erated, care being taken preferably to notoverheat the iron or manganese oxidto such an extent that its preferred.amorphous condition is lostsothat it does not effect as rapid catalysis.The regenerated lime, especially if not over-heated, may be used againand again.

In place of carbon monoxid or water gas, producer gas, etc., the vaporsof oil, for example, may be mingled with steam and passed over the limeto effect decom osition, thereby liberating hydrogen'bothn rom the oiland the water, forming first carbon. monoxid and then carbon dioxidwhich is. absorbed by the lime,. Or other alkali such as caustic soda orsoda lime may be used, or forma-tes or oxalates also obtain undercertain circumstances.

To recapitulate, my invention relates to the process of making hydrogenby reactmg with carbon monoxid on water vapors at a temperature ofpreferably approximately 500 C. in the presence of calcium oxid orequivalent absorben'tsof carbon dioxid,preferably passing the reactinggases as a 001mter current against or in contact with a travelingstreamof the lime material, preferably proportioning the ratio of the rbonmonoxid and water vapors in the ratio of 114:.

or higher, but preferably between the limits with an oppositelytraveling o'f.1 4 and 1:5; in removing the carbonated material andpreferably calcining same to eliminate carbon dioxid and in again usingthe regenerated lime material for: carrying out the aforesaid reaction;said limematerial preferably containing 5% or so of a a catalyst such asiron. oxid or manganese oxid preferably in an amorphous form, prefer-.ably precipitated on the particles of lime.

In the latter case the catalytic material may be added to powderedquicklimebymeans of an aqueous solution of a salt such'as sulfate oracetate of iron or manganese so thatprecipitation of the catalyst on theparticles of lime ensues, thereby securing a very desirable contact anddistribution. 'Preferably .an excess of quicklime over that required tocompletely absorb the carbon dioxid derived from the monoxid isemployed. 25-50% excess of calcium oxid may be used as thereby betterand more effective conversion is obtained. The gas and vapor passing offat His cooled, waterpreferably removed by condensation and the gas ifdesired is further dried in any suitable manner. The removal of the lastportions or traces of carbon monoxid or nitrogen may be had by passingthe gas over heated calcium carbid. What I claim is:

1. The herein described process of producing" ydrogen-containing gaseswhich comprises passing a-mixture comprising a carbon-containing gas andsteam,'in proportions equivalent to about four to five times as'muchsteam as would correspond to the production of CO and} hydrogen intocontact with a material comprising lime and about 5% of acatalytically-active metal oxid, While'maintai ned at a. temperature ofing gas with water vapor so as to give a proportion of said monoxid tovsaid water vapor of between 1:4 and 1:5, in passing said mixture as acounter current and in incomprises mixing a carbon monoxid-containtimatecontact'with a traveling streamof quick lime'material in a finelydivided condition and admixed with catalytic material comprisingametallic oxid, and in maintaining the temperature of the reactingmaterials at approximately 500 C.-;'whereby said carbon .monoxid' issubstantially converted into carbon dioxid and unites with the quicklime material to form carbonate of lime.

.4. The process of making hydrogen which comprises passing a. carbonmonoxid-conlytic material taining gas substantially free from 'nitrogenin the presence of water vapor into contact with a nearly horizontalmoving body of a carbon dioxid absorbent and catalytic materialmaintained at a reacting temperature; in collecting the hydrogen formed,and in substantially freeing the same from water vapor.

-5. The process of making hydrogen which comprises passlng a carbonmonoxid-containing gas in the presence of water vapor into contact witha moving body of a carbon dioxid absorbent and precipitatedcatamaintained at a reacting temperature; in collecting the hydrogenformed, and in substantially freeing the same from water vapor.

6. The process of making hydrogen which comprises passing a carbonmonoxid-containing gas in the presence of a material excess of watervapor into contact with a nearly horizontal moving body of a carbondioxid absorbent in excess and catalytic material maintained at areacting temperature; in collecting the hydrogen formed, and'insubstantially freeing the same from water vapor.

7 The process of making gases containing hydrogen which comprisespassing a carbon monoxid-containing gas in the presence' of water vaporinto contact with a moving body of a carbon dioxid absorbent '5 andcatalytic material maintained at a reacting temperature.

8. A process of producing gases contain-. ing free hydrogen whichcomprises passing a mixture comprising a carbon containing gas havingreducing properties and steam, in such' proportions as to correspond toa material excess of steam over the quantity theoretically necessary forthe production of a gas mixture consisting essentially of carbon dioxidand hydrogen, in contact with a material comprising lime and acatalytically active metal oxid, While said material is maintained at atemperature of approximately 500 to 550 C.

9. A process of producing gases containing hydrogen which comprisespassing a mixture comprising ,carbon monoxid and steam in substantiallythe proportions of 4 to 5 molecules of steam to 1 molecule of carbonmonoxid into contact with a material comprising lime and iron oxid,While maintaining said material at a temperature of about.500 to 550 C.

Signed at Montclair, sex and State of New Jersey, of June, A. D. 1913.

- CARLETON ELLIS.

Witnesses Y B. M. ELLIS, F. GARBUTT.

in the county of Esthis 3rd day

